Phthalocyanine ink-jet dyes

ABSTRACT

Phthalocyanine compounds of Formula (1) have utility as colorants in inks for ink-jet printing, where Formula (1) represents:                    
     which includes all IJP-effective forms of such compounds; and in which: 
     M represents a metal or H; 
     A represents C 1 4 alkylene; 
     Pc represents a phthalocyanine nucleus of Formula (2):                    
     D represents NR 4 R 5  or SC 1-4 alkyleneSO 3 H; 
     R 1 , R 2  and R 3 each independently represents H or C 1-4 -alkyl; 
     R 4  represents H,; or C 1-4 -alkyl optionally substituted by hydroxy; 
     R 5  represents C 1-4 alkyl optionally substituted by hydroxy and/or morpholino; or 
     R 4  and R 5  together with the N atom to which they are attached form a morpholino ring; and 
     x+y+z represents an average of from 3 to 4.

This invention relates to compounds, to ink compositions comprising themand to the use of such inks in ink jet printing (“IJP”). IJP is anon-impact printing technique in which droplets of ink are ejectedthrough a fine nozzle onto a substrate without bringing the nozzle intocontact with the substrate.

There are many demanding performance requirements for colorants and inksused in IJP. For example they desirably provide sharp, non-featheredimages having good water-fastness, light-fastness and optical density.The inks are often required to dry quickly when applied to a substrateto prevent smudging, but they should not form a crust over the tip of anink jet nozzle because this will stop the printer from working. The inks10 should also be stable to storage over time without decomposing orforming a precipitate which could block the fine nozzle.

The applicant has discovered that certain phthalocyanine compounds haveparticular utility as colorants for use in IJP as they may produceprints with unexpectedly good optical density, light fastness and/orwater fastness.

According to the present invention there is provided a compound ofFormula (1):

which includes all IJP-effective forms of such compounds; and in which:

M represents a metal or H;

A represents C₁₋₄alkylene;

Pc represents a phthalocyanine nucleus of Formula (2):

D represents NR₄R₅ or SC₁₄alkyleneSO₃H;

R₁, R₂ and R₃each independently represents H or C₁₋₄-alkyl;

R₄represents H, or C₁₄-alkyl optionally substituted by hydroxy;

R₅ represents C₁₋₄alkyl optionally substituted by hydroxy and/ormorpholino; or

R₄ and R₅ together with the N atom to which they are attached form amorpholino ring; and

x+y+z represents an average of from 3 to 4.

When M is a metal it is preferably selected from Li, Na, K, Mg, Ca, Ba,Al, Si, Sn, Pb, Rh, Sc, Ti, V, Cr, Mn, Fe, Co, Ni and Cu, morepreferably from Sc, Ti, Va, Cr, Mn, Fe, Co, Zn, Ni and Cu and especiallyfrom Ni and Cu.

Preferred dyes of Formula (1) are those in which M is Cu, R₁, R₂ and R₃are H, D is NR₄R₅, in which R₄ is H and R₅ is CH₂CH₂OH, A is —CH₂CH₂—,(x+y)>z especially x is 1.3, y is 1.2 and z is 1.5.

Any radical group mentioned herein as a substituent refers to amonovalent radical unless otherwise stated. A group which comprises achain of three or more atoms signifies a group in which the chain may bestraight or branched or the chain or part of the chain may form a ring.For example, an alkyl group may comprise: propyl which includes n-propyland isopropyl; butyl which includes n-butyl, sec-butyl, isobutyl andtert-butyl; and an alkyl group of three or more carbon atoms maycomprise a cycloalkyl group. The total number of certain atoms isspecified herein for certain substituents, for example C_(1-n)alkyl,signifies an alkyl group having from 1 to ‘n’ carbon atoms. The term‘halo’ as used herein signifies fluoro, chloro, bromo and iodo radicals.

According to a further feature of the present invention there isprovided an ink effective for use in ink jet printing (IJP-effective)comprising a medium and a colorant comprising a IJP-effective compoundof Formula (1) as defined herein. Preferably in the ink of the presentinvention the compounds of Formula (1) comprise dyes, more preferablydyes comprising a predominately cyan colour.

The term ‘IJP effective’ (for example with reference to the inks,compositions, ingredients, substituents and/or compounds describedherein) will be understood to mean effective for use in ink-jet printingby for example: providing desirable properties to the ink, beingcompatible with any inert carriers and/or diluents suitable forformulating such inks, being compatible with ink jet printers and/orcapable of being ink-jet printed. In relation to the processes describedherein effective compounds are those which will undergo the specifiedreactions to form the compounds of the present invention. To beparticularly acceptable for use in IJP compounds of Formula (1) may beAmes negative.

IJP-effective forms of the compounds of Formula (1) may be selected fromone or more of the following (including mixtures thereof andcombinations thereof in the same molecular moiety): salts,stereoisomers, zwitterions, polymorphic forms, complexes andisotopically substituted forms. Specific compounds of Formula (1)comprise those compounds exemplified herein; all IJP-effective saltsthereof, preferably their potassium, sodium or ammonium salts; andIJP-effective mixtures thereof.

Compounds of Formula (1) may be in the form as shown in the structuresherein (i.e. free acid form) but are preferably in the form of salts.Salts of Formula (1) may be formed from one or more organic and/orinorganic bases and/or acids and compounds of Formula (1) which areacidic and/or basic (for example acid and/or base addition salts). Saltsof Formula (1) comprise all IJP-effective salts that may be formed frommonovalent and/or multivalent acids and/or bases. Salts of Formula (1)also comprise all enantiomeric salts formed with IJP-effective chiralacids and/or bases and/or any mixtures of enantiomers of such salts (forexample racemic mixtures). The dyes may be converted into a salt usingknown techniques. The present invention comprises all IJP-effectivesalts of Formula (1) and IJP-effective mixtures thereof.

Preferred salts of Formulae (1) are alkali metal salts (especiallylithium, sodium and potassium salts), and optionally substitutedammonium salts (especially salts with ammonia and volatile amines). Morepreferred salts are those with a cation of formula ⁺NT₄ where each T isindependently H or optionally substituted alkyl, or two groupsrepresented by T are H or optionally substituted alkyl and the remainingtwo groups represented by T, together with the N atom to which they areattached, form a 5 or 6 membered ring (preferably a morpholine, pyridineor piperidine ring). Most preferably each T is independently H orC₁₋₄alkyl, especially H. CH₃ or CH₃CH₂, more especially H. Examples ofcations which are IJP-effective comprise: ^(+NH) ₄, morpholinium,piperidinium, pyridinium, (CH₃)₃N⁺H, (CH₃)₂N⁺H₂, H₂N⁺(CH₃)(CH₂CH₃),CH₃N⁺H₃, CH₃CH₂N⁺H₃, H₂N⁺(CH₂CH₃)₂, CH₃CH₂CH₂N⁺H₃, CH₃CH₂CH₂N⁺H₃,(CH₃)₂CHN⁺H₃, N⁺(CH₃)₄, N⁺(CH₂CH₃)₄, N-methyl pyridinium, N,N-dimethylpiperidinium and N,N-dimethyl morpholinium.

Certain compounds of Formula (1) may exist as one or more stereoisomers,for example, enantiomers, diastereoisomers, geometric isomers,tautomers, conformers and/or combinations thereof within the samemoiety. The present invention comprises all IJP-effective stereoisomersof compounds of Formula (1) and IJP-effective mixtures thereof.

Certain compounds of Formula (1) may exist as one or more zwitterions,for example, moieties which comprise two or more centres of ioniccharge. The present invention comprises all IJP-effective zwitterions ofFormula (1) and IJP-effective mixtures thereof.

Certain compounds of Formula (1) may exist as one or more polymorphs,for example, phases, crystalline forms, amorphous forms, solidsolutions, interstitial compounds and/or any mixtures thereof. Thepresent invention comprises all IJP-effective polymorphs of Formula (1)and IJP-effective mixtures thereof.

Certain compounds of Formula (1) may exist in the form of one or moreother complexes in addition to the metal complexes shown herein, forexample, chelates, solvates, other organometallic complexes, and/orcomplexes with other IJP-effective ligands. Such complexes may be formedbetween an suitable substrate in which the compound of Formula (1)and/or the substrate may act as a ligand. The substrate may comprise oneor more solvents to form solvates. The complexes may benon-stoichiometric, for example if the complex is a hydrate it maycomprise a hemihydrate, monohydrate and/or dihydrate. The presentinvention comprises all IJP-effective complexes of Formula (1) andIJP-effective mixtures thereof.

Certain compounds of Formula (1) may exist as one or more isotopic formsin which one or more atoms in Formula (1) comprise one or more isotopes.The natural ratios of various isotopes may be altered by suitable means,for example certain ¹²C atoms in certain compounds of Formula (1) may besubstantially replaced by the less common ¹⁴C and/or ¹³C isotopes.Optionally certain isotopic forms of Formula (1) may be radio-active.Certain of the isotopic forms of Formula (1) may be used as means forselective imaging in imaging devices (for example devices using X-rays,positron emission tomography and/or nuclear magnetic resonance); and/oras tools to investigate the mode of action of compounds of Formula (1)in IJP. The present invention comprises all IJP-effective, isotopicforms of Formula (1) and IJP-effective mixtures thereof.

The present invention relates to all compounds of Formula (1) even thosewhich may not be directly effective for use in IJP because they exhibitundesirable properties.

Such compounds may nevertheless have utility in the field of the presentinvention for example as intermediates in the preparation and/orpurification of IJP-effective compounds of Formula (1) and/or asresearch tools and/or diagnostic aids in relation to iJP.

Compounds of Formula (1) may be prepared the methods described below andby other suitable methods analogous to those described in the art forsimilar phthalocyanine compounds.

A preferred method for preparing dyes of Formula (1) comprises thefollowing steps:

a) Preparing a compound of formula MPc(SO₂Cl)_(x+y+)using methods knownper se. A preferred method preparing a compound of formulaMPC(SO₂Cl)_(x+y+z) comprises heating (preferably for about 1 to about 24hours), a metal-free or metal containing phthalocyanine (optionallycomprising one to four sulpho groups) with chlorosulphonic acid,preferably at a temperature above about 60° C., more preferably aboveabout 100° C., most preferably from about 120° C. to about 165° C.Optionally this may be followed by heating (preferably for about 10 toabout 48 hours, more preferably for about 10 to about 30 hours), thephthalocyanine with PCI₃, preferably at lower temperature than with thechlorosulphonic acid, more preferably from about 80° C. to about 105° C.

b) Condensing the compound of formula MPc(SO₂Cl)_(x+y+z) in water at 0°C. with a halo amine of formula NHR₃AX, where X is halo, preferablychloro. More preferably the haloamine is in the form of itshydrochloride salt.

c) Treating the halogenated adduct from step ID) with ammonium hydroxideand warming the reaction mixture to 40° C. for about 1 hour.

d) Reacting the material from step c) with an amine of formula NHR₄R₅ ora thiol of formula HSC₁₋₄alkyleneSO₃H, in aqueous solution at about 70°C. for about 3 hours to produce a dye of Formula (1).

The reactions leading to the formation of the present compounds may beperformed under conditions that have been described in the art andcompounds of Formula (1) may be isolated by known methods such as spraydrying or precipitation followed by filtration.

Preferably the ink of the present invention comprises:

(a) from 0.01 to 30 parts of an IJP-effective compound of Formula (1);and

(b) from 70 to 99.99 parts of a liquid medium or a low melting pointsolid medium; wherein all parts are by weight and the number of parts of(a)+(b)=100.

The number of parts of component (a) is preferably from 0.1 to 20, morepreferably from 0.5 to 15, and especially from 1 to 5 parts. The numberof parts of component (b) is preferably from 99.9 to 80, more preferablyfrom 99.5 to 85, especially from 99 to 95 parts.

When the medium is a liquid, preferably component (a) is completelydissolved in component (b). Preferably component (a) has a solubility incomponent (b) at 20° C. of at least 10%. This allows the preparation ofconcentrates which may be used to prepare more dilute inks and reducesthe chance of the colorant precipitating if evaporation of the liquidmedium occurs during storage.

Preferred liquid media include water, a mixture of water and an organicsolvent and an organic solvent free from water.

When the medium comprises a mixture of water and an organic solvent, theweight ratio of water to organic solvent is preferably from 99:1 to1:99, more preferably from 99:1 to 50:50 and especially from 95:5 to80:20. Preferably the organic solvent comprising the mixture of waterand organic solvent is a water-miscible organic solvent or a mixture ofsuch solvents. The liquid medium may comprise water and preferably twoor more, more preferably from 2 to 8, water-soluble organic solvents.

Preferred water-miscible organic solvents comprise:

C₁₋₆alkanols, preferably methanol, ethanol, n-propanol, isopropanol,n-butanol, sec-butanol, tert-butanol, n-pentanol, cyclopentanol and/orcyclohexanol;

linear amides, preferably dimethylformamide and/or dimethylacetamide;

ketones and/or ketone-alcohols, preferably acetone, methyl ether ketone,cyclohexanone and/or diacetone alcohol;

water-miscible ethers, preferably tetrahydrofuran and/or dioxane;

diols, preferably C₂-₁₂diols (for example pentane-1,5-diol, ethyleneglycol, propylene glycol, butylene glycol, pentylene glycol, hexyleneglycol and/or thiodiglycol) and/or oligo- and/or poly-aikyleneglycols(for example diethylene glycol, triethylene glycol, polyethylene glycoland/or polypropylene glycol);

triols, preferably glycerol and/or 1,2,6-hexanetriol;

C₁₋₄alkyl ethers of diols, preferably monoC₁₋₄alkyl ethers ofC₂₋₁₂diols: {for example 2-methoxyethanol, 2-(2-methoxyethoxy)ethanol,2-(2-ethoxyethoxy)-ethanol, 2-[2-(2-methoxyethoxy)ethoxy]-ethanol,2-[2-(2-ethoxyethoxy)-ethoxy]-ethanol and/or ethyleneglycol monoallylether};

cyclic amides, preferably 2-pyrrolidone, N-methyl-2-pyrrolidone,N-ethyl-2-pyrrolidone, caprolactam and/or 1,3-dimethylimidazolidone;

cyclic esters, preferably caprolactone;

sulphoxides, preferably dimethyl sulphoxide and/or sulpholane; and/or

all IJP-effective mixtures thereof.

More preferred water-soluble organic solvents are selected from:

cyclic amides (e.g. 2-pyrrolidone, N-methyl-pyrrolidone andN-ethyl-pyrrolidone);

diols, (e.g. 1,5-pentane diol, ethyleneglycol, thiodiglycol,diethyleneglycol and triethyleneglycol);

C₁₋₄alkyl ethers of diols (e.g. 2-methoxy-2-ethoxy-2-ethoxyethanol); andall IJP-effective mixtures thereof.

A preferred liquid medium comprises:

(a) from 75 to 95 parts water; and

(b) from 25 to 5 parts in total of one or more solvents selected from:

diethylene glycol, 2-pyrrolidone, thiodiglycol, N-methylpyrrolidone,cyclohexanol, caprolactone, caprolactam and pentane-1,5-diol;

where the parts are by weight and the sum of the parts (a)+(b)=100.

Another preferred liquid medium comprises:

(a) from 60 to 80 parts water;

(b) from 2 to 20 parts diethylene glycol; and

(c) from 0.5 to 20 parts in total of one or more solvents selected from:

2-pyrrolidone, N-methylpyrrolidone, cyclohexanol, caprolactone,caprolactam, pentane-1,5-diol and thiodiglycol;

where the parts are by weight and the sum of the parts (a)+(b)+(c)=100.

Examples of further IJP-effective media for inks of the presentinvention comprise a mixture of water and one or more organic solventsare described in U.S. Pat. No. 4,963,189, U.S. Pat. No. 4,703,113, U.S.Pat. No. 4,626,284 and EP 0425150-A.

When the liquid medium comprises an organic solvent free from water,(i.e. less than 1% water by weight) the solvent preferably has a boilingpoint of from 30° to 200° C., ore preferably of from 40° to 150° C.,especially from 50 to 125° C. The organic solvent may bewater-immiscible, water-miscible or a mixture of such solvents.Preferred water-miscible organic solvents comprise any of thosedescribed above and mixtures thereof. Preferred water-immisciblesolvents comprise aliphatic hydrocarbons; esters (for example ethylacetate) chlorinated hydrocarbons (for example dichloromethane), ethers(for example diethyl ether) and mixtures thereof.

When the liquid medium comprises a water-immiscible organic solvent,preferably it comprises a polar solvent (for example a C₁₋₄alkanol) toenhance the solubility of the dye in the liquid medium. It is especiallypreferred that where the liquid medium is an organic solvent free fromwater it comprises a ketone (especially methyl ethyl ketone) and/or analcohol (especially a C₁₋₄alkanol, more especially ethanol or propanol).

The organic solvent free from water may be a single organic solvent or amixture of two or more organic solvents. It is preferred that when themedium is an organic solvent free from water it is a mixture of 2 to 5different organic solvents. This allows a medium to be selected whichgives good control over the drying characteristics and storage stabilityof the ink.

Ink media comprising an organic solvent free from water are particularlyuseful where fast drying times are required and particularly whenprinting onto hydrophobic and non-absorbent substrates, for exampleplastics, metal and glass.

Preferred low melting solid media have a melting point in the range from60° C. to 125° C. Suitable low melting point solids include long chainfatty acids or alcohols, preferably those with C₁₈₋₂₄chains, andsulphonamides. The dye of Formula (1) may be dissolved in the lowmelting point solid or may be finely dispersed in it.

The ink may also contain additional components conventionally used ininks for IJP, for example viscosity and surface tension modifiers,corrosion inhibitors, biocides, kogation reducing additives andsurfactants which may be ionic or non-ionic.

A further aspect of the invention provides a process for printing animage on a substrate comprising applying to the substrate by means of anink jet printer, an ink of the present invention as defined herein.

The ink jet printer preferably applies the ink to the substrate in theform of droplets which are ejected through a small orifice onto thesubstrate. Preferred ink jet printers are piezoelectric ink jet printersand thermal ink jet printers. In thermal ink jet printers, programmedpulses of heat are applied to the ink in a reservoir by means of aresistor adjacent to the orifice, thereby causing the ink to be ejectedin the form of small droplets directed towards the substrate duringrelative movement between the substrate and the orifice. Inpiezoelectric ink jet printers the oscillation of a small crystal causesejection of the ink from the orifice.

The substrate is preferably paper, plastic, a textile, metal or glass,more preferably paper, an overhead projector slide or a textilematerial, especially paper. Preferred papers are plain or treated paperswhich may have an acid, alkaline or neutral character.

A further aspect of the present invention provides a paper, an overheadprojector slide or a textile material printed with an ink and/or acolorant as defined herein and/or by means of a process as definedherein.

When the substrate is a textile material the ink according to theinvention is preferably applied thereto by:

i) applying the ink to the textile material using an ink jet printer;and

ii) heating the printed textile material at a suitable temperature,preferably from 50° C. to 250° C., to fix the ink on the material.

Preferred textile materials are natural, synthetic and semi-syntheticmaterials. Examples of preferred natural textile materials include wool,silk, hair and cellulosic materials, particularly cotton, jute, hemp,flax and linen. Examples of preferred synthetic and semi-syntheticmaterials include polyamides, polyesters, polyacrylonitriles andpolyurethanes.

Preferably the textile material has been treated with an aqueouspre-treatment composition comprising a thickening agent and optionally awater-soluble base and a hydrotropic agent and dried prior to step i)above.

The pre-treatment composition preferably comprises a solution of thebase and the hydrotropic agent in water containing the thickening agent.Particularly preferred pre-treatment compositions are described morefully in EP 0534660-A.

The invention is further illustrated by the following Examples in whichall parts and percentages are by weight unless otherwise stated.

EXAMPLE 1

Preparation of

a) Preparation of CuPc(SO₂Cl)₄

Copper phthalocyanine (115 g) was added in portions to stirredchlorosulphonic acid (308 ml) over 30 minutes keeping the temperaturebelow 50° C. The mixture was stirred for 30 minutes before being heatedgradually to 140° C., at which temperature it was stirred for 3 hours.The mixture was cooled to 40° C. and phosphorus trichloride (52.5 g) wasadded in portions over 30 minutes, whilst the temperature was kept below50° C. The mixture was stirred overnight at room temperature and thencooled to 0° C. and poured onto a mixture of ice (700 g), water (700 g),concentrated hydrochloric acid (40 ml) and sodium chloride (100 g). Themixture was stirred at 0° C. for 30 minutes. The precipitated productwas collected by filtration at reduced pressure and washed with ice-coldhydrochloric acid solution (0.5 M, 1.5 l) to obtain a paste ofCuPc(SO₂Cl)₄.

b) Reaction with β-chloroethylammonium chloride to obtain:

A solution of β-chloroethylammonium chloride (34.7 9) in water (1 l) wascooled to 0° C. and the sulphonyl chloride paste from step a) was added.The pH of the mixture was adjusted to 7 to 8 with dilute ammoniumhydroxide solution. The mixture was stirred at 0° C. for 1 hour, heatedto 40° C. and stirred at that temperature for a further hour and thencooled to room temperature. The pH of the mixture was adjusted to 1.5with concentrated hydrochloric acid and the mixture was stirred for 1hour. The precipitated product was collected by filtration at reducedpressure and washed with dilute hydrochloric acid solution (0.5 M, 1.5l) to obtain the above chloro compound.

c) Reaction with 4-(2-aminoethyl)morpholine to produce Example 1

A solution of the chloro compound from step b) (40 g) and4-(2-aminoethyl)morpholine (27 ml) in water (350 ml) was stirred at 70°C. for 4 hours. Sodium chloride (25% w/v) was added and the pH of themixture was adjusted to 6.0 with concentrated hydrochloric acid. Theresultant precipitate was collected by filtration at reduced pressureand washed with acid brine (25%, 100 ml, pH 4) and methanol (100 ml) toobtain as the product the title dye.

EXAMPLE 2

Preparation of

Steps a) and b) are carried out as Example 1 above.

c) Reaction with ethanolamine to produce Example 2

A solution of the chloro compound from step b) of Example 1 (40 g) andethanolamine (13 g) in water (300 ml) was stirred at 70° C. for 4 hours.The product was then isolated as described above in Example 1 step c) toproduce the title dye.

EXAMPLE 3

Preparation of

Steps a) and b) are carried out as Example 1 above.

c) Reaction with diethanolamine to produce Example 3

A solution of the chloro compound from step b) of Example 1 (40 g) anddiethanolamine (21 g) in water (300 ml) was stirred at 70° C. for 4hours. The product was then isolated as described above in Example 1step c) to produce the title dye.

EXAMPLE 4

Preparation of

Steps a) and b) are carried out as Example 1 above.

c) Reaction with morpholine to produce Example 4

A solution of the chloro compound from step b) of Example 1 (40 g) andmorpholine (18 ml) in water (300 ml) was stirred at 70° C. for 4 hours.The product was then isolated as described above in Example 1 step c) toproduce the title dye.

EXAMPLE 5

Preparation of

Steps a) and b) are carried out as Example 1 above.

c) Reaction with 3-mercaptopropane sulphonic acid to produce Example 5

A solution of the chloro compound from step b) of Example 1 (28 g) andthe sodium salt of 3-mercaptopropane sulphonic acid (26.7 g) in water(300 ml) was stirred at 50° C. and pH 9 for 7 hours. The product wasthen isolated as described above in Example 1 step c) [with themodification that the pH of the mixture after adding sodium chloride wasadjusted to 1.0 with concentrated hydrochloric acid] to produce thetitle dye.

Salts

The exemplified sodium salts (examples 1 to 5) prepared as describedabove, may be used after suitable purification directly in inkformulations as described below or may be were converted to otherIJP-effective salts as follows. Each example was dissolved in distilledwater. The solution was filtered and the volume of the filtrate adjustedto 4 litres. The solution was desalinated by reverse osmosis. Thedissolved sodium salt may be converted into another IJP-effective salt[e.g. the potassium salt] by passing the solution through anion-exchange column comprising Dowex HGRW resin saturated with asuitable solution [e.g. potassium hydroxide solution (5% w/v)]. Thesolution of the (e.g. potassium) salt thus obtained was then filteredand water was evaporated form the filtrate to yield a purified saltsuitable for use directly in an ink as described below.

Inks

The effectiveness in ink jet printing of compounds of Formula (1) wasdemonstrated as follows. Inks separately comprising each exemplified dyewere prepared by dissolving 2 parts of the sodium salt, prepared asdescribed above, in 98 parts of a mixture of water and 2-pyrrolidone (ina respective ratio of 90:10 by volume). The inks were printed ontogelatin paper (obtained from Felix Schoeller) using a thermal ink-jetprinter to give bright cyan prints which had excellent light fastness.

Further inks comprising the exemplified dyes may be may be prepared asdescribed in the following tables in which the number in the firstcolumn (headed Ex. no.) denotes the example number of dye to be used inthe ink. The dye may be in its free acid form and/or in the form of anyIJP-effective salt (e.g. sodium, potassium or ammonium salt). Numbersquoted in the second column onwards refer to the number of parts of therelevant ingredient and all parts are by weight. The inks may be appliedto paper by thermal or piezo ink jet printing.

The following abbreviations are used in the tables:

PG=propylene glycol;

DEG=diethylene glycol;

NMP=N-methyl pyrollidone;

DMK=dimethylketone;

NaST=Na stearate

IPA=isopropanol;

MEOH=methanol;

2P=2-pyrollidone;

MIBK=methylisobutyl ketone;

CET=cetyl ammonium bromide;

TBT=tertiary butanol;

TDG=thiodiglycol;

BDL=butane-2,3-diol;

PHO Na₂HPO₄;

P12=propane-1,2-diol.

CHL=cyclohexanol; and

PDL=pentan-1,5-diol.

TABLE I Ex. no. Dye Water PG DEG NMP DMK MEOH 2P MIBK 1 2.0 80 5 6 4 5 210.0 85 3 3 3 5 1 3 2.1 91 8 1 4 2.4 75 3 4 5 6 5 5 5.1 96 4 1 1.8 80 515 2 2.6 84 11 5 3 3.3 80 2 10 2 6 4 5.4 69 2 20  2 1 3 3 5 7.0 70 15 310

TABLE II Ex. No. Dye Water PG DEG NMP NaOH Na ST IPA 2P MIBK 1 2.0 70 76 3 2 2 4.0 65 4 6 0.7 5 3 1.0 50 4 5 1 4 3.1 86 5 2 0.2 4 5 5 1.1 81 29 0.5 0.5 9

TABLE III Ex. no. Dye Water PG DEG NMP DMK IPA MEOH 2P MIBK 1 3.1 86 5 45 2 1.1 81 9 9 3 2.5 60 4 15 3 3 6 10 5 4 4 3.2 65 5 4 6 5  4 6 5 5 10.080 2 6 2 5 1 4

TABLE IV Ex. no. Dye Water PG DEG NMP DMK NaOH Na ST IPA 1 3.0 90 5 50.2 2 5 65 5 20 10  3 4.1 80 5 2 10 0.3 4 10.8 90 5 5 5 12.0 90 7 0.3 3

TABLE V Ex. no. Dye Water PG DEG NMP CET PHO 2P P12 1 3.0 80 15 0.2 5 29.0 90 5 1.2 5 3 2.5 90 6 4 0.12 4 3.1 82 4 8 0.3 6 5 10.0 91 6 3 1 5.078 5 11 6 2 6.0 63 3 4 2.0 3 3.0 72 15 0.8 3 4 5.4 86 5 7 3.0 7 5 2.0 9010 10

TABLE VI Ex. no. Dye Water PG DEG NMP CET TBT TDG 1 1.5 85 5 5 0.15 5.00.2 2 9.0 90 5 5 0.3 3 2.0 90 10 4 2.0 88 10 5 5.5 70 4 4 0.4 3

TABLE VII Ex. no. Dye Water PG DEG NMP TBT TDG BDL PHO 2P 1 0.9 85 10 50.2 2 4.0 70 10 4 1 4 3 2.2 75 4 10 3 2 6 4 9.0 76 9 7 3.0 0.95 5 5 2.170 5 5 5 0.2 0.1 5 0.1 5

TABLE VIII Ex. no. Dye Water PG DEG NMP TBT TDG 2P 1 3.0 55 5 2.0 3 26.0 65 4 0.1 5 3 5.0 78 5 12 5 4 8.0 70 2 8 15 5 5 10.0 80 8 12

TABLE IX Ex. no. Dye Water PG DEG NMP BDL PHO 2P P12 1 10.0 75 3 5 3 3 12 3.5 80  6 5 3 2.0 90 7 7 0.5 4 6.0 65 5 2 5 4.0 70 10 4 1 4 11 

TABLE X Ex. No. Dye Water PG DEG NMP CET TBT TDG BDL PHO 2P 1 1.5 80 1 23 0.5 0.4 7 2 10  2 3.0 60 4 2.0 0.5 3 4.5 90 3 6 7.0 1 3 2 4 3.0 95 7 43 0.5 5 2.1 70 5 5 5 0.1 0.2 0.1 5 0.1 5

TABLE XI Ex. no. Dye Water PG DEG NMP CHL PHO 2P PDL 1 7.0 75 3 5 3 3 12 3.5 60 2 5 3 2.0 90 7 7 1.5 2 4 6.0 65 5 2 5 4.0 70 5 4 1 4 12

What is claimed is:
 1. A compound of Formula (1):

which includes all IJP-effective forms of such compounds; and in which:M represents a metal or H; A represents C₁₋₄alkylene; Pc represents aphthalocyanine nucleus of Formula (2):

D represents SC₁₋₄alkyleneSO₃H; R₁, R₂ and R₃each independentlyrepresents H or C₁₋₄-alkyl; and x+y+z represents an average of from 3 to4; provided that z and y are not zero.
 2. An ink effective for use inink jet printing, comprising a medium and a colorant comprising anIJP-effective compound of Formula (1) as claimed in claim
 1. 3. Aprocess for printing a substrate with an ink as claimed in claim 2,using an ink-jet printer.
 4. A substrate printed with an ink as claimedin claim 2, the substrate selected from one or more of: paper, anoverhead projector slide and a textile material.
 5. A process for thecolouring a textile material with an ink as claimed in claim 2, theprocess comprising the steps of: i) applying the ink to the textilematerial by ink-jet printing; and ii) heating the textile material at asuitable temperature to fix the ink on the material.
 6. A compound asclaimed in claim 1 wherein M is Ni or Cu.
 7. A compound as claimed inclaim 1 or claim 6 wherein M is Cu; R₁, R₂ and R₃ are all H; A is C₂H₄;and D is SC₃H₆SO₃H.
 8. A compound as claimed in claim 1 or claim 6wherein (x+y)>z.
 9. A compound as claimed in claim 1 or claim 6 whereinx is 1.3, y is 1.2 and z is 1.5.
 10. An ink according to claim 2 whereinthe medium comprises water and an organic solvent.